Efficiency of man-made and/or natural organic based animal manure fertilizers by liberating the bound nutrients (macro and micro) through the use of organic, non-aqueous liquid delivery formulations containing organic poly (organicacids) and/or their salts

ABSTRACT

The present invention relates to improving the efficacy of man-made and/or natural organic-based animal manure fertilizers by administration of an organic solvent formula containing polyorganic acids and/or their salts. The formulation liberates nutrient(s) that are normally bound in the soil as insoluble salts and complexes. These delivery formulations also provide an environmentally sound and inherently safe solvating system that improves diffusion of polyorganic acids to the granule fertilizer. These delivery formulations enable safe storage, transport and subsequent application or blending with solid or liquid fertilizers. The combined formulation and fertilizer can be applied to soil to provide improved efficacy of fertilizer by liberating nutrients bound in the soil for uptake by plant life.

This application is a continuation of and claims priority under 35 USC120 to U.S. application Ser. No. 15/893,593 filed Feb. 10, 2018, whichin turn is a continuation of and claims priority to U.S. applicationSer. No. 14/740,327 filed Jun. 16, 2015, which in turn claims priorityunder 35 USC 119(e) to U.S. Provisional No. 61/991,680 filed May 12,2014.

FIELD OF INVENTION

The present invention relates to improving the efficiency of man-madeand/or natural organic-based animal manure fertilizers by administrationof an organic solvent formula containing poly (organic acids) and/ortheir salts that liberates the nutrient(s) bound in the soil asinsoluble salts and complexes. The compositions and methods of thepresent invention result in a flowable, low moisture liquid that can bereadily mixed with liquid fertilizers or applied evenly on the surfaceof solid fertilizer granules.

BACKGROUND OF THE INVENTION

Agriculture currently utilizes fertilizers to deliver the needednutrients (macro and micro) to plants through the application of thesefertilizers to the soil. Fertilizers can be formulated as man-madeproducts and/or natural organic based animal manure. These nutrients areabsorbed from soil by plants to sustain their growth. Phosphorous issecond to nitrogen as the most limiting macronutrient. In the case ofphosphorus fertilizer, 40% of landscape soil is considered to containinadequate levels of phosphorus for woody plant growth. Moreover, mostof the phosphorus is largely inaccessible as it is in a form that is notsoluble in water (and thus are not available to plants). In some cases,only 0.01% of the total soil phosphorus is in the form of a watersoluble ion, the only form which can be absorbed by the plant. Adequateand accessible soil phosphorus is essential for optimal crop yields.Phosphorus enables a plant to store and transfer energy, promotes root,flower and fruit development, and allows early maturity. Phosphorus isalso involved in many processes critical to plant development such asphotosynthesis where plants utilize organic phosphorous compounds whenconverting sunlight to energy. Without enough phosphorus present in thesoil, plants cannot grow sufficient root structure, which is key to theplant's ability to absorb water and nutrients from the soil. Moreover,woody plants without sufficient root structure cannot maintain anequilibrium between roots and shoots, which is key to surviving drought,windy weather, and/or pests. Other nutrients such as calcium, magnesium,sulfur, manganese, zinc, iron, and the like can also be locked into thesoil in insoluble salts and complexes. Often, these nutrient-insolublesalts and complexes contain a phosphate anion that results from thereaction of fertilizer components containing mono and/or di-ammoniumphosphates with metal cations when the fertilizer is applied to thesoil. The presence of water in the soil provides an ideal medium,promoting the reaction that results in the formation of these insolublesalts and complexes.

Because fertilizers containing phosphorus are important in agriculture,it would seem that using more stable cations (such as sodium and/orpotassium phosphates) versus the largely unstable ammonium phosphatewould tend to limit the formation of these insoluble salts andcomplexes, leading to less pollution (and more available phosphorous forplants). However, in practice, the relatively high solubility of theammonia, sodium and/or potassium phosphate cause them to be releasedinto our waterways, creating deleterious effects. One such effect ofwater soluble phosphorus salts that is washed into lakes or rivers iseutrophication. Eutrophication occurs in a lake or river whenundesirable algae and/or underwater weeds grow as the result ofincreased nutrient supply. This generally causes low water oxygenconcentrations and clogged waterways, which sometimes leads to the lossof aquatic animals (such as fish) and other aquatic plants.

To address this issue, some states (in the US) and countries arebeginning to regulate the usage of phosphorus in fertilizers to decreaseeutrophication. Thus, it would desirable to optimize fertilizerperformance so that the requisite amount of nutrients (includingphosphorous) be delivered to soil in a timely manner thereby allowingplants to grow at levels that are economically and environmentallyviable. Accordingly, a fertilizer additive that will allow the slowconversion and release of the requisite nutrients (that may be in theform of insoluble salts and complexes) will not only decrease the degreeof pollution, but it will also reduce the cost of the fertilizer byimproving efficiency in a time sensitive manner allowing the requisitenutrients to be released over a longer duration of time. The advantageof this additive would be that nutrients would be more readily availableover longer time periods, resulting in plants that are not only healthyand grow well, but ultimately produce higher yields.

DESCRIPTION Of RELATED ART

To present, multiple products have been developed to try to increase theefficiency of the release of phosphorus in fertilizer as well as therelease of nutrients bound in the soil as insoluble salts and complexes.The mechanisms of action for the vast majority of these products aresimilar. When a fertilizer containing phosphorus is applied to the soil,most of the phosphorous is in a water-soluble phosphate ion form, theonly form of phosphorus that is readily absorbed by the plant. In thepresence of moisture/water, however, these soluble phosphate anions willbe attached to metal ions such as calcium, magnesium, iron, aluminum andthe like. These salts have very low solubility in water and thus, cannotbe readily absorbed by plants. Polymers with negatively charged ions canchelate/complex with the metal ions resulting in a freed, water-solublephosphate anion with the cation (such as calcium, magnesium, sulfur,manganese, zinc, iron, and the like) complexed with the poly (organicacid). Both the phosphate anion and the poly (organic acid) complexedcation are now more readily available to plants for absorption. Variousmethods or variations of the above described mechanism are listed in thepatents below, which are incorporated by reference in their entireties.These methods have been proposed and developed for the slow release ofnutrients bound in the soil in the form of insoluble salts andcomplexes.

Boehmke (U.S. Pat. No. 4,839,461) teaches how to synthesize and use aman-made version of polyaspartic acid and its salts that preventsincrustations formed by the metal ions that are responsible for hardwater. Boehmke further discloses that this compound can be used as afertilizer.

Ashmead (U.S. Pat. No. 4,172,072) discloses the use of protein sourcesto form metal proteinates, which are in a biologically accepted form.Others reveal carboxylic containing entities either as monomers or aspolymers such as Danzig (U.S. Pat. No. 4,799,953), which utilizespolymers of thiolactic acid or thioglycolic acid and thiolactic acid,dithiobispropanoic acid and dithiobisacetic acid, Kinnersley (U.S. Pat.No. 4,813,997), which utilizes glycolic and/or lactic acid, and Young(U.S. Pat. Nos. 4,863,506 and 5,059,241) that disclose that d-lacticacid can promote increased plant growth, increased concentration ofchlorophyll, and increase the rate of root formation.

Gill (U.S. Pat. No. 5,047,078) utilized scale inhibiting compounds suchas those based on polymers of ethylenically unsaturated carboxylic acidsand/or maleic acid/anhydride monomers and/or phosphorous based chelatorssuch as dihydroxy ethylidene diphosphonic acid to make availablenutrients bound in the soil as insoluble salts and complexes resultingin increased growth and yields.

Kinnersley (U.S. Pat. Nos. 5,350,735 and 5,593,947) and Koskan (U.S.Pat. Nos. 5,783,523 and 5,814,582) teach using poly (organic) acids likepoly (amino acids) such as poly(aspartic) acid to enhance fertilizeruptake and promote plant growth.

Sanders (U.S. Pat. Nos. 6,753,395, 6,756,461, 6,818,039, and 8,041,995)demonstrate that man-made poly (organic acids) based on maleic, itaconicand/or citraconic anhydrides can be utilized to enhance nutrient uptakeby plants.

Sanders (U.S. Pat. Nos. 8,016,907 and 8,025,709) shows the importance ofhaving a quick drying product that one can apply to the surface ofgranules for fertilizer. Sanders accomplishes this by using 10-50% of avolatile alcohol such as methanol.

Many of these disclosures are now available in the marketplace. A 30%aqueous solution of sodium salt of a maleic itaconic copolymer, (U.S.Pat. No. 6,515,090 to Sanders), is marketed under the brand name Avail.Another polymer containing 40% sodium poly-lysine aqueous solution ismarketed as P-Max in the US market. A similar polymer, poly-aspartatewas also used for this purpose (U.S. Pat. No. 5,350,735 to Kinnersley).In the market, a composition that contains 30% aqueous solution ofsodium poly-aspartate is marketed as X10D (Flexible SolutionInternational). All of these products have been shown to increase theefficiency of phosphorus fertilizer in their field tests and havegenerally been shown to be biodegradable.

However, all these products suffer from the same drawback. Mostfertilizers tend to be solid granules and water soluble. Theabove-stated inventions are almost exclusively based on aqueoussolutions and/or they contain water. When these products are applied tosolid fertilizer granules, they quickly dissolve the surface granulesleaving most sub-surface granules untouched. In many cases, the solidfertilizers applied with a coating of an aqueous solution/dispersion canform agglomerations clogging field application equipment making itdifficult to ensure an even distribution of fertilizer on fields. Ifthese granules of fertilizer have also been coated with amoisture-sensitive urease inhibitor like an alkyl thiophosphorictriamide, the presence of moisture from water based products will resultin degradation of these important urease inhibitors, negativelyimpacting/limiting their performance. Some innovations have to be soldas a costly, separate application product because of the presence ofwater. The newer technologies utilize volatile organic solvents topromote quick drying, but utilizing this approach increases thevolatility of organic compounds in the process such as by using a lowflash point alcohol such as methanol. In some instances, this leads tothe loss of additive, making the fertilizer additive more expensive. Toaddress these problems, there is a need for a non-aqueous liquidformulation that can easily and evenly coat fertilizer granules withoutresulting in agglomeration. The non-aqueous liquid formulation shouldcontain components that will liberate bound nutrients, be safe, have lowmoisture and be environmentally friendly while simultaneously providingmore flexibility for fertilizer manufacturers to produce productsdesigned for the particular soil requirements that occur in differentregions of the world.

SUMMARY OF THE INVENTION

In an embodiment, the present invention relates to a series of organicsolvent systems that dissolve poly (organic acids) and/or their saltsand results in a product that can coat fertilizer granules evenly andeconomically and impart to the fertilizer the vital property ofliberating bound nutrients when applied to the soil.

In embodiments, the present invention also relates to improved solventformulations for Poly (organic acids) for application to man-made and/ornatural organic based animal manure fertilizers. In a variation, poly(organic acids) may be solid chemical substances, which are dissolved ina suitable solvent to allow application at low levels in the field.Additionally, solutions of poly (organic acids) may be desirable whenthey are to be incorporated as components of a granular mixedfertilizer, such that they can be deposited as a coating in a controlledand homogenous layer. In one embodiment, this invention proposesformulations of mixtures containing aprotic and/or protic solvents,which are more environmentally friendly and are safe for manufacturers,transporters and others who work with/handle thecompositions/formulations.

In one embodiment, improved delivery formulations have been developedthat deliver effective levels of poly (organic acids) and/or their saltsthat liberate nutrients bound in the soil as insoluble salts andcomplexes over time increasing their longevity in the soil. It has beenfound that the delivery formulations of the present invention provide aliquid vehicle to deliver an even, non-clumping application of thedesired poly (organic acids) and/or their salts to the fertilizergranule. These new delivery formulations for poly (organic acids) and/ortheir salts are non-water-containing organic solvents that improve thestorage life of fertilizers containing urease inhibitors such as alkylthiophosphoric triamides relative to those formulations containinggreater than 1% water. In fact, because of the present invention, onecan now combine poly (organic acids) and/or their salts to liberatebound nutrients, nitrification inhibitors, and crease inhibitors in oneproduct by either blending together the dispersions of each or bycombining the dispersions of both inhibitors in the same improvedsolvent formulation(s). In embodiments, the present invention relates tocompositions/formulations of poly (organic acids) and/or their salts inorganic solvent based solvating systems that:

-   -   Are environmentally safe;    -   Have flashpoints above 145° F.;    -   Are inherently rated safe for contact with humans and animals;    -   Provide stable solutions of poly (organic acids) or their salts        at 1-50% in solution to storage temperatures down to at least        10° C.;    -   Provide improved even application to fertilizer granules while        not causing clumping of the granules;    -   Will not detrimentally impact the stability of alkyl        thiophosphoric triamides.

In one embodiment, it has been discovered that while various organicsolvents might meet some of the above criteria, the delivery system ofthe present invention can be optimized to provide a formulation with ahigh concentration of poly (organic acids) and/or their salts whilemaintaining a low chill point by combining two or more organic solventsin a solvating system. In one embodiment, one process for preparing theformulations of the present invention is to heat the combined solventsto temperatures approaching about 100° C. and charging the poly (organicacids) and/or their salts in a combined level of 10-60% of the totalformula composition, which can be dissolved in the solvent mixture withmoderate agitation.

In one embodiment, the present invention relates to an effective solventcombination that comprises dimethyl sulfoxide (DMSO), which, can be usedin combination with another organic-solvent delivery system that has alow chill point and good solvating properties. Besides the advantageslisted above, DMSO also has the advantage of potentially serving as asource of the important nutrient sulfur.

DETAILED DESCRIPTION

Improved delivery formulations have been developed that delivereffective levels of poly (organic acids) and/or their salts thatliberate nutrients bound in the soil as insoluble salts and complexes.These delivery formulations not only provide a liquid vehicle to deliveran even, non-clumping application of the desired poly (organic acids)and/or their salts to the fertilizer granule, but it has been discoveredthat formulations based on non-aqueous solvating systems improve thestorage life of the important urease inhibitors, such as alkylthiophosphoric triamides. Alkyl thiophosphoric triamides, if present incombination with poly (organic acids) and/or their salts as contained inthe present formulations, have been shown to be extremely effectiveurease inhibitors but suffer from degradation upon storage if exposed tomoisture contained in these current technologies. Thus, in oneembodiment the present invention relates to compositions that aresubstantially free of water.

The delivery system of the present invention is based on (an) improvedsolvent formulation(s) that is used to solubilize one or more poly(organic acid) and/or its salts and can contain one or more of thefollowing:

-   -   Urease inhibitor(s);    -   Nitrification inhibitor(s);    -   Additives such as but not limited to surfactants, buffers,        fragrance/odor masking agents, colorants, micro-nutrients,        and/or flow modifiers such as silica.

In one embodiment, the compositions of the present invention contain oneor more poly (organic acid(s)) and/or its salts, one or morenitrification inhibitor(s) and one or more urease inhibitor(s). Thesecompositions optionally contain one or more of surfactants, buffers,fragrance/odor masking agents, colorants, micro-nutrients, and/or flowmodifiers.

In one embodiment, the improved solvent formulations of the presentinvention meet one or more of the following criteria: They are:

-   -   environmentally safe;    -   thermally safe because they have flashpoints above 145° F.;    -   inherently rated safe for contact with humans and animals;    -   able to maintain poly(organic acids) and/or their salts at        levels of 1-50% in solution to temperatures down to at least        10° C. This ability means that these compositions have        relatively long storage lives;    -   able to provide improved and even application to fertilizer        granules of poly(organic acids) and or their salts while not        causing clumping of the granules;    -   substantially free of water which also provides improved        stability of urease inhibitors, primarily alkyl        thiophosphoramides such as N-(n-butyl) thiophosphoric triamide        (NBPT).

In one embodiment, the present invention relates to liquid formulationscontaining sodium polyaspartate (polymer weight=1,500 to 3000 oralternatively about 1500-2750 or alternatively 1750-2500 oralternatively about 2000-2250). In an embodiment, the formulations canbe made by dissolving the sodium polyaspartate into a a) protic solventconsisting of 1) an alcohol or polyol from the family of alkylene andpoly(alkylene) glycols. Exemplary compounds that can be used includeethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butyleneglycol, trimethylol propane trimethylol ethane, pentaerythritol,sorbitol and sorbitan, glucose, fructose, galactose, isopropylideneglycerol and/or glycerin and/or 2) alkylene glycol alkyl ethers such astripropylene glycol methyl ether, tripropylene glycol butyl ether, b)mixed with aprotic component(s) such as 1) Dimethyl Sulfoxide and or 2)dialkyl, diaryl, or alkylaryl sulfoxide(s) having the formulaR₁—SO—R₂,

-   -   wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl and    -   wherein R₂ is ethyl, n-propyl, phenyl or benzyl        and/or 3) alkylene carbonates such as ethylene carbonate,        propylene carbonate and/or butylene carbonate and/or 4) polyols        capped with acetate or formate wherein the polyol portion may be        one or more of ethylene glycol, 1,3 propylene glycol, 1,2        propylene glycol, butylene glycol, trimethylol, propane        trimethylol ethane, pentaerythritol, sorbitol and sorbitan,        glucose, fructose, galactose and/or glycerin 4) alkylene glycol        alkyl ethers acetates such as tripropylene glycol methyl ether        acetate, tripropylene glycol butyl ether acetate and/or 5)        isophorone 6) ethyl, propyl, or butyl lactate 7)        dimethylsuccinate, dimethyl adipate, diethyl glutarate, and/or        dimethyl glutarate.        Additionally, the delivery formulations of the present invention        may contain one or more of the following:    -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the        formulations;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules;    -   buffering agents    -   one or more urease inhibitors in an organic liquid dispersing        system; and/or    -   one or more nitrification inhibitors in an organic liquid        dispersing system;

In one embodiment, the solvating system of the present invention is anorganic solvent or a blend of organic solvents, which may include butare not limited to one or more of the following:

dimethyl sulfoxide, dimethylacetamide, dimethylformamidehexamethylphosphoramide, propylene carbonate, ethylene carbonate,butylene carbonate, 1,2-dimethyloxethane, 2-methoxyethyl ether,cyclohexylpyrrolidone, ethyl lactate, 1,3 dimethyl-2-imidazolidinone,limonene, acetate and/or fumerate capped polyols, and include but arenot limited to the following polyols, alcohols or esters:

-   -   ethylene glycol, propylene glycol, butylene glycol, trimethylol        propane, pentaerythritol, glycerine, isopropylidene glycerol,        trimethylol ethane, polyethylene glycol, polypropylene glycol,        polyethylene/polypropylene glycol copolymer, tripropylene glycol        methyl ether, tripropylene glycol butyl ether, propylene        carbonate, isophorone, dimethylsuccinate, dimethyl adipate,        diethyl glutarate, dimethyl glutarate.

Additionally, the delivery formulation(s) may contain the following:

-   -   a food coloring or dye that may be used to improve the visual        evidence of complete coverage and serve as a visual marker    -   scents or masking agents to improve the odor of the formula    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules    -   buffering agents

In an embodiment, the formulation may contain one or more poly (organicacids) and/or their salts based on the following monomers either ashomopolymers, copolymers and/or terpolymers at effective levels in thedelivery system wherein they may be present in an amount between about5-50% of the total amount.

-   -   aspartic acid    -   glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid    -   acrylic acid

In an embodiment, NBPT is added to an 80/20 to 20/80 mix of dimethylsulfoxide (DMSO) and ethylene glycol and subsequently polyaspartic acid(or its salt or ester) is added with the polyaspartate being about 5-45%by weight of the total composition. In an embodiment, polyaspartate isadded, under agitation, to the combined solvents that have been heatedin a mixing vessel at a desired temperature of about 0° C. to 150° C.,or alternatively at a temperature of about 10° C. to 120° C. oralternatively, at a temperature of about 20° C. to 100° C., oralternatively between about 50° C. and 100° C. and mixed until the polyaspartate acid is completely dissolved. The heated mix vessel, in thisembodiment, may be jacketed and the temperature carefully controlled. Inan embodiment, the mixing action should allow complete mixing withouttoo much aeration. In a variation, the heating may be accomplished usinghot water or low pressure steam to control any hot spots on walls of thevessel to prevent heat degradation. At this stage, the mixture can becooled to about 35° C. and then the NBPT can be added and agitated untilcompletely dissolved. The mixture can be cooled to 25° C. or below andone or more of the following may be added, if desired:

-   -   a food coloring or dye that improves the visual evidence of        complete coverage and serves as a visual marker    -   scents or masking agents that improve the odor of the formula    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance on        insuring even distribution and of fertilizer granules in the        soil: and/or    -   buffering agents.

It should be recognized that in the temperature ranges given above, theranges are set so as to allow adequate dissolution of the variouscompounds. The inventors recognize that should a compound be added thathas temperature stability issues, the additions may be under reducedpressure conditions so as to prevent temperature sensitive degradationsof the one or more compounds but at the same time allowing theirdissolution in the organic solvent.

In another embodiment, poly aspartate ammonia salt may be present at a10-50% level in a solution mix of DMSO and ethylene glycol at a ratio ofabout 80/20 to 20/80. In this embodiment, poly aspartate ammonia saltmay be added, under agitation, to the combined aprotic solvents thathave been heated in a mixing vessel at a desired temperature of about 0°C. to 60° C., or alternatively, at a temperature of about 10° C. to 50°C. and, alternatively, to a temperature of about 20° C. to 40° C. andmixed until the poly aspartate ammonia salt is completely dissolved.Also in this embodiment, the heated mix vessel may be jacketed andtemperature controlled. In an embodiment, the mixing action may allowcomplete mixing without too much aeration. In an embodiment the mixingaction might include one or more of high shear devices such as a cowlesblade, a colloid mill, a rotor stator and/or a ball mill. The heatingmay be accomplished using hot water and/or low pressure steam to controlany hot spots on the walls of the vessel, which can prevent heatdegradation. At this stage, the mixture can be cooled to about 25° C. orbelow, and one or more of the following additives may be added, ifdesired:

-   -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and/or    -   buffering agents.

In an embodiment, poly aspartate or its acid may be added at a 5-50%level relative to a composition comprising ethylene glycol. In thisembodiment, poly aspartate acid may be added, under agitation, to thesolvents that have been heated in a mixing vessel at a temperature ofabout 0° C. to 60° C. and mixed until the poly aspartate is completelydissolved. In an embodiment, the heated mix vessel may be jacketed andthe temperature controlled. In a variation, the mixing action allowscomplete mixing without too much aeration. The heating can beaccomplished using hot water and/or low pressure steam to control anyhot spots on the walls of the vessel to prevent heat degradation. Atthis stage, the mixture may be cooled to 25° C. or below and one or moreof the following may be added, if desired:

-   -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and/or    -   buffering agents

In an embodiment, poly aspartate ammonia salt may be incorporated at a5-50% level to ethylene glycol. In this embodiment, poly aspartateammonia may be added, under agitation, to the combined aprotic solventsthat have been heated in a mixing vessel at a temperature of about 0° C.to 60° C. and mixed until the polyaspartate ammonia salts are completelydissolved. The heated mix vessel may be jacketed and the temperaturecontrolled. In a variation, the mixing action allows complete mixingwithout too much aeration. The heating can be accomplished using hotwater or low pressure steam to control any hot spots on the walls of thevessel to prevent heat degradation. At this stage, the mixture may becooled to 25° C. or below and one or more of the following may be added,if desired:

-   -   a food coloring or dye may be used to improve the visual        evidence of complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and/or buffering agents

In an embodiment, polymaleic anhydride may be produced in a solvent suchas xylene using an organic peroxide using a process known to those ofskill in the art. The resulting solvated poly (organic acid) can undergosolvent replacement by charging an aprotic solvent such as 1) dimethylsulfoxide and/or 2) a dialkyl, diaryl, or alkylaryl sulfoxide having theformulaR₁—SO—R₂,

-   -   wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl and    -   wherein R₂ is ethyl, n-propyl, phenyl or benzyl

and/or 3) alkylene carbonate such as ethylene carbonate, propylenecarbonate and/or butylene carbonate and/or 4) polyol capped with acetateor formate with the polyol portion comprised of ethylene glycol, 1,3propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol,propane trimethylol ethane, pentaerythritol, sorbitol and sorbitan,glucose, fructose, galactose and/or glycerin 4) alkylene glycol alkylethers acetates such as tripropylene glycol methyl ether acetate.

One may then begin to strip the unwanted solvent out either bydifferential boiling points or by the use of a vacuum (such as by use ofa rotary evaporator) until the unwanted solvent is reduced to a levelthat is less than about 1%. The polymaleic anhydride can be neutralizedin the new solvating system to a desired pH with NaOH, KOH, NH₃, K₃,K₂CO₃, Na₂CO₃, KHCO₃ and/or NaHCO₃. If water resulting fromneutralization or from the addition of aqueous solutions of thesealkalis is present, the water can be removed by stripping (such as byuse of a rotary evaporator) through temperature or through lowertemperature/vacuum to ensure a low moisture formula.

Other known means of removing water can be used such as by use ofmolecular sieves or by addition of a drying agent (such as Na₂SO₄ orMgSO₄) and subsequent filtration.

In an embodiment, potassium polyaspartate can be incorporated in amountsthat are about 10-45% of a formulation mixture that also containsethylene and propylene glycol at ratios from about 80/20 to 20/80. In anembodiment, potassium polyaspartate may be added, under agitation, tothe combined organic liquids that have been heated in a mixing vessel ata temperature of about 0° C. to 150° C., or alternatively to atemperature of about 40° C. to 130° C., or alternatively to atemperature of about 60° C. to 120° C., or alternatively to atemperature of about 70° C. to 100° C. and mixed until the potassiumpolyaspartate is completely dissolved. In an embodiment, the heated mixvessel may be jacketed and the temperature carefully controlled. In avariation, the mixing action allows complete mixing without too muchaeration. Heating can be accomplished using hot water or low pressurestream to control any hot spots on the walls of the vessel to preventheat degradation to the potassium polyaspartate. Alternatively, themixing may be done at reduced pressure or the action can be performed inan inert atmosphere (such as but not limited to nitrogen, argon and/orcarbon dioxide) to limit thermal or oxidative degradation. At this stage(after the initial mixing), the mixture may be cooled to about 25° C. orbelow and one or more of the following may be added, if desired:

-   -   one or more urease inhibitors dispersed in an organic liquid        dispersing system;    -   one or more nitrification inhibitors dispersed in an organic        liquid dispersing system;    -   a food coloring or dye to improve the visual evidence of        complete coverage and serve as a visual marker;    -   scents or masking agents to improve the odor of the formula;    -   nonionic, anionic, cationic, zwitterionic, and/or amphoteric        surfactants to improve formula application performance of        fertilizer granules; and/or    -   buffering agents.

In another variation, the mixture of poly (organic acid)(s) in anorganic-liquid can be placed under high shear agitation such as but notlimited to an overhead agitator equipped with a cowles blade or a rotorstator mixer to assist in reducing viscosity of the mixture.

In an embodiment, the present invention relates to making thecompositions and fertilizer granules and liquid additives of the presentinvention. In a variation a polysuccinimide is heated to 100-160° C. inthe presence of an excess of a protic solvent resulting in the formationof a polyaspartate-ester dispersed in the protic solvent which issubsequently saponified with the addition of NaOH, KOH, NH₃, K₂CO₃,Na₂CO₃, KHCO₃ and NaHCO₃ resulting in a stable dispersion of a salt ofpolyaspartic acid in an organic-liquid.

In an embodiment, the present invention relates to making thecompositions and fertilizer granules and liquid additives of the presentinvention. In a variation a polysuccinimide is heated to 40-80° C. inthe presence of an aprotic solvent and mixed until the polysuccinimideis completely dissolved. NaOH, KOH, NH₃, K₂CO₃, Na₂CO₃, KHCO₃ or NaHCO₃are charged and mixed. The vessel is placed under vacuum to remove anyresidual water formed or introduced.

In an embodiment, the present invention relates to making thecompositions and fertilizer granules and liquid additives of the presentinvention. In a variation a reactive monomer or a blend of reactivemonomers such as but not limited to aspartic acid and/or glutamic acidis heated to 100-185° C. in the presence of an excess of protic solventresulting in the formation of a poly (organic-ester) which issubsequently saponified with the addition of NaOH, KOH, NH₃, K₂CO₃,Na₂CO₃, KHCO₃ or NaHCO₃ resulting in a stable dispersion of a salt ofpoly (organic acid) in an organic-liquid.

In an embodiment, the present invention relates to making thecompositions and fertilizer granules and liquid additives of the presentinvention. In a variation a reactive monomer or a blend of reactivemonomers such as but not limited to acrylic acid, maleic anhydride,maleic acid, citraconic anhydride itaconic anhydride and/or itaconicacid glutamic acid is heated to 60-140° C. in the presence of excessprotic solvent and with a free radical catalyst such as but not limitedto ammonium persulfate, benzoyl peroxide and/or di-tort butyl peroxideresulting in the formation of a poly (organic-ester) which issubsequently saponified with the addition of NaOH, KOH, NH₃, K₂CO₃,Na₂CO₃, KHCO₃ or NaHCO₃ resulting in a stable dispersion of a salt ofpoly (organic acid(s)) in an organic-liquid.

In an embodiment, polyacrylic acid may be produced in a solvent such asmethyl ethyl ketone using a peroxide catalyst and a process known tothose experienced in the art. The resulting solvated poly (organic acid)can undergo solvent replacement by charging an aprotic solvent from thegroup comprised of 1) dimethyl sulfoxide and/or 2) dialkyl, diaryl, oralkylaryl sulfoxide having the formulaR₁—SO—R₂,

-   -   wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl and    -   wherein R₂ is ethyl, n-propyl, phenyl or benzyl

and/or 3) alkylene carbonate such as ethylene carbonate, propylenecarbonate and/or butylene carbonate and/or 4) a polyol capped withacetate or formate with the polyol portion being one or more of ethyleneglycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol,trimethylol, propane trimethylol ethane, pentaerythritol, sorbitol andsorbitan, glucose, fructose, galactose and/or glycerin 4) alkyleneglycol alkyl ethers acetates such as tripropylene glycol methyl etheracetate.

Subsequently, one can then begin to strip the unwanted solvent outeither by differential boiling points or by the use of vacuum until theunwanted solvent is reduced to a level that is less than about 1%. Thepolyacrylic acid can be neutralized in the new solvating system to adesired pH with NaOH, KOH, NH₃, K₂CO₃, Na₂CO₃, KHCO₃ and NaHCO₃. Ifwater resulting from neutralization or from the addition of aqueoussolutions of these alkalis is present, the water can be removed bystripping (such as by use of a rotary evaporator) through temperature orthrough lower temperature/vacuum to ensure a low moisture formula.

In an embodiment, one or more additional urease inhibitors, one or moreadditional poly (organic acids) and/or one or more additionalnitrification inhibitors may be added to formulations of the presentinvention. In an embodiment, the additional urease inhibitor, poly(organic acids) and/or nitrification inhibitors may be dissolved in themixture. In an embodiment, useful mixtures may be prepared either bydilution or mixture with liquid fertilizers.

Examples of the present formulation include liquid mixtures of urea orsolid mixtures that may be made by contacting the mixture with solidfertilizers such as granular urea. In an embodiment, coated granularurea can be prepared by using any commercially available equipment inwhich granular product can be mixed or sprayed with a liquid. A flowaid, silicas or surfactants such as soap or nonionic surfactants may beadded prior to addition of the liquid for improved dispersability.

The resulting product(s) can be applied to soil in either a liquidand/or a granular form to provide improved nutrient retention in thesoil for uptake for plant life.

In an embodiment, the one or more nitrification inhibitors comprisesdicyanoamides, one or more of the poly (organic acids) polyaspartic acidand/or its salts, and the one or more urease inhibitors comprisesphosphoramides.

In an embodiment, the composition may comprise one or more ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, and/or flow modifiers.

In an embodiment, the composition is substantially free of water.

In an embodiment, the present invention relates to fertilizer additives.In one embodiment, the fertilizer additive comprises one or morenitrification inhibitors, one or more poly (organic acids) and one ormore urease, inhibitors.

In an embodiment, the present invention relates to making compositionsand fertilizer additives. In one embodiment, the present inventionrelates to a method of making a composition to be added to a fertilizer,wherein the method comprises:

heating a mixture comprising one or more poly (organic acid);

cooling the mixture to a temperature that optionally allows addition ofone or more of surfactants, buffers, fragrance/odor masking agents,colorants, micro-nutrients, and/or flow modifiers.

In one variation of the method, the method comprises further adding thecomposition to a fertilizer.

In an embodiment, the present invention relates to a compositioncomprising one or more poly (organic acids) and/or their salts in anorganic liquid solvating system comprising one or more protic solvents;

wherein the one or more protic solvent(s) comprise one or more of 1) analcohol or polyol from the family of C₁₋₁₀ alkanols and poly(C₁₋₁₀alkylene) glycols, 2) an alkylene glycol selected from the groupconsisting of ethylene, propylene, and butylene glycol, 3) glycerin,isopropylidene glycerol, trimethylol propane, triethanol propane,pentaerythritol 4) an alkanolamine selected from the group consisting ofethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and triethanolamine, 5) alkylene glycol alkylethers selected from the group consisting of tripropylene glycol methylether, and tripropylene glycol butyl ether

wherein the one or more polyorganic acids and/or their salts is amonomer homopolymer, a copolymer and/or a terpolymer or one or more ofthe following:

-   -   aspartic acid    -   glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid; or    -   acrylic acid;        wherein the polyorganic acids are present in an amount that is        about 5-50% of the total composition.

In a variation, the composition may contain one or more protic solventsthat comprise ethylene glycol, propylene glycol, butylene glycol,glycerine, tripropylene glycol and/or their methyl ethers.

In a variation, the one or more protic solvents comprise between about90/10 to 10/90% of the composition.

In a variation, the one or more polyorganic acids is potassium aspartatein a formulation wherein potassium aspartate is present in an amountthat is between about 10-45% of a total formulation amount and theformulation also contains a mixture of ethylene glycol and propyleneglycol in ratios that are between about 20/80 to 80/20.

In an embodiment, the composition may further comprise one or more ofsurfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, dispersed urease inhibitor(s) dispersed nitrificationinhibitor(s) and/or flow modifiers.

In a variation, the composition is substantially free of water.

In an embodiment, the present invention relates to a compositioncomprising one or more polyorganic acids and/or their salts in anorganic liquid solvating system comprising a mixture of aprotic andprotic solvents

wherein the aprotic solvents is/are

1) dimethyl sulfoxide,

2) dialkyl sulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide havingthe formulaR₁—SO—R₂,

wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl and R₂ is ethyl,n-propyl, phenyl or benzyl,

3) alkyl carbonate selected from the group consisting ethylene,propylene and butylene carbonates,

4) ethyl, propyl, or butyl lactate

5) isophorone and/or dimethylsuccinate, diethyl glutamate, dimethyladipate, dimethyl glutarate and the protic component(s) is/are one ormore of a) an alcohol or polyol selected from the group consisting ofC₁₋₁₀ alkanols and poly(C₁₋₁₀ alkylene) glycols, b) an alkylene glycolselected from the group consisting of ethylene, propylene, and butyleneglycol, c) glycerin, isopropylidene glycerol d) an alkanolamine selectedfrom the group consisting of ethanolamine, diethanolamine,dipropanolamine, methyl diethanolamine, monoisopropanolamine andtriethanolamine, e) alkylene glycol alkyl ethers selected from the groupconsisting of tripropylene glycol methyl ether, and tripropylene glycolbutyl ether.

In a variation, the composition may contain one or more polyorganicacids and/or their salts and the polyorganic acids and/or their saltsare a monomer, a homopolymer, a copolymer and/or a terpolymer comprisingone or more of

-   -   aspartic acid    -   glutamic acid    -   maleic anhydride    -   itaconic anhydride    -   citraconic anhydride    -   citric acid; or    -   acrylic acid        wherein the one or more polyorganic acids are present at about        5-50% of a total composition.

In an embodiment, the composition may contain (a) protic solvent(s) thatis(are) ethylene glycol, propylene glycol, butylene glycol, glycerine,tripropylene glycol methyl ether

In a variation, the aprotic solvent(s) is(are) dimethyl sulfoxide,propylene carbonate, dimethylsuccinate, diethyl glutarate, or dimethylglutarate.

In a variation, the ratio of protic solvent to aprotic solvent isbetween about 90/10 to 10/90% and a total of the organic liquidsolvating system is between about 10 to 90% of a final composition.

In a variation, the one or more polyorganic acids and their saltscomprise sodium aspartate in a formulation wherein sodium aspartate ispresent in an amount that is between about 10-45% of a total formulationamount and the formulation also contains a) ethylene glycol and/orpropylene glycol and b) propylene carbonate in a ratio that is betweenabout 20/80 to 80/20.

In a variation, the composition is substantially free of water.

In an embodiment, the present invention relates to a fertilizeradditive, which comprises one or more polyorganic acids and/or theirsalts in an organic liquid solvating system comprising one or moreprotic solvents or a mixture of aprotic and protic solvents,

wherein the aprotic solvent is 1) dimethyl sulfoxide, 2) a dialkylsulfoxide, diaryl sulfoxide, or an alkylaryl sulfoxide having theformulaR₁—SO—R₃,

wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl,

and R₂ is ethyl, n-propyl, phenyl or benzyl,

3) an alkyl carbonate selected from the group consisting of ethylene,propylene and butylene carbonates, 4) ethyl, propyl, or butyl lactate 5)isophorone and/or dimethylsuccinate, dimethyl adipate, diethylglutarate, dimethyl glutarate, and the protic component(s) is/are one ormore of 1) an alcohol or polyol from the family of C₁₋₁₀ alkanols andpoly(C₁₋₁₀ alkylene) glycols, 2) an alkylene glycol selected from thegroup consisting of ethylene, propylene, and butylene glycol, 3)glycerin, isopropylidene glycerol, 4) an alkanolamine selected from thegroup consisting of ethanolamine, diethanolamine, dipropanolamine,methyl diethanolamine, monoisopropanolamine and triethanolamine, and/or5) alkylene glycol alkyl ethers selected from the group consisting oftripropylene glycol methyl ether, and tripropylene glycol butyl ether.

In a variation, the fertilizer may comprise one or more polyorganicacids and/or their salts, which are a monomer, a homopolymer, acopolymer or a terpolymer of one or more of the following:

-   -   Aspartic acid    -   Glutamic acid    -   Maleic Anhydride    -   Itaconic Anhydride    -   Citraconic anhydride    -   Citric acid    -   Acrylic acid;        wherein the one or more polyorganic acids is present at an        amount that is about 5-50% of a total composition.

In a variation, the fertilizer additive may further comprising one ormore nitrification inhibitors wherein the one or more nitrificationinhibitors is selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide, thiourea,1-mercapto-1,2,4-triazole, 3,4-dimethylpyrazole phosphate, and2-amino-4-chloro-6-methylpyrimidine.

In an embodiment, the fertilizer additive may further comprise one ormore urease inhibitors wherein the one or more urease inhibitors isselected from the group consisting of phosphoric triamides,thiophosphoric triamides and alkylated thiophosphoric triamides, whereinthe alkylated thiophosphoric triamides has one or more alkyl groups thatindependently contain between 1 and 6 carbon atoms.

In a variation, the fertilizer additive may comprise one or morenitrification inhibitors wherein the one or more nitrificationinhibitors comprise dicyanoamide, the one or more polyorganic acidscomprise polyaspartic acid and the one or more urease inhibitorscomprise phosphoric triamides. Alternatively, the one or more ureaseinhibitors may comprise a phosphoramide.

In an embodiment, the present invention relates to a method of making acomposition to be added to a fertilizer comprising:

heating a mixture comprising one or more polyorganic acids in an organicliquid solvating system comprising one or more protic solvents orcomprising a mixture of aprotic and protic solvents

wherein the aprotic solvent is 1) dimethyl sulfoxide, 2) dialkylsulfoxide, diaryl sulfoxide, or an alkyl aryl sulfoxide having theformulaR₁—SO—R₂,

wherein R₁ is methyl, ethyl, n-propyl, phenyl or benzyl

and R₂ is ethyl, n-propyl, phenyl or benzyl,

3) an alkyl carbonate selected from the group consisting of ethylene,propylene and butylene carbonates, 4) an ethyl, propyl, or butyl lactate5) an isophorone and/or dimethylsuccinate, dimethyl adipate, diethylglutarate, dimethyl glutarate,

and the protic component(s) is/are one or more of 1) an alcohol orpolyol from the family of C₁₋₁₀ alkanols and poly(C₁₋₁₀ alkylene)glycols, 2) an alkylene glycol selected from the group consisting ofethylene, propylene, and butylene glycol, 3) glycerin, isopropylideneglycerol, 4) an alkanolamine selected from the group consisting ofethanolamine, diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and triethanolamine and/or 5) alkylene glycol alkylethers selected from the group consisting of tripropylene glycol methylether, and tripropylene glycol butyl ether;

and cooling the mixture to a temperature that optionally allows additionof one or more of surfactants, buffers, fragrance/odor masking agents,colorants, micro-nutrients, dispersed urease inhibitor(s), dispersednitrification inhibitor(s) and/or flow modifiers.

In an embodiment, the method may further comprise adding the compositionto a fertilizer.

In a variation, the method may comprise one or more polyorganic acidsand/or their salts wherein they are a homopolymer, a copolymer, or aterpolymer comprising one or more of the following:

-   -   Aspartic acid    -   Glutamic acid    -   Maleic Anhydride    -   itaconic Anhydride    -   Citraconic anhydride    -   Citric acid    -   Acrylic acid;        wherein the one or more polyorganic acids are present at a level        that is between about 5-50% of a total composition.

In a variation, the method may use dispersed nitrification inhibitorsthat is/are one or more members selected from the group consisting of2-chloro-6-trichloromethyl)pyridine, 4-amino-1,2,4-6-triazole-HCl,2,4-diamino-6-trichloromethyltriazine CL-1580, dicyandiamide, thiourea,1-mercapto-1,2,4-triazole, and 2-amino-4-chloro-6-methylpyrimidine,3,4-dimethylpyrazole phosphate.

In an embodiment, the method may comprise one or more dispersed ureaseinhibitors wherein they are one or more members selected from the groupconsisting of phosphoric triamides, thiophosphoric triamides andalkylated thiophosphoric triamides, wherein the alkylated thiophosphorictriamides has one or more alkyl groups that independently containbetween 1 and 6 carbon atoms.

In a variation, the method may comprise a dispersed nitrificationinhibitor and a dispersed urease inhibitor wherein the dispersednitrification inhibitor comprises dicyanoamide and the dispersed ureaseinhibitor comprises phosphoric triamides. Alternatively, the dispersedurease inhibitor may comprise a phosphoramide.

In a variation, the method may use a composition that is substantiallyfree of water. Substantially free of water means less than about 1%water.

The following Examples are presented to illustrate certain embodimentsof the present invention:

Example 1

400 grams of ethylene glycol was charged to a vessel, placed understrong agitation and then heated to 60° C. 222.2 grams ofpolyaspartate-potassium salt/90% NVS was then slowly charged to thevessel and mixed until completely dissolved. Once dissolved, the mixturewas placed under high shear agitation by using an overhead mixerequipped with a cowles blade while maintaining the batch temperature at60-80° C. for 1 hour. After one hour the vessel was sealed and a vacuumof 200 mm or less was pulled to remove water. The mixture was cooled to<30° C. and then packaged off in an appropriate container.

Example 2

120 grams of Example 1 was heated to 60° C., placed under agitation andthen 80 grams of propylene glycol was charged to the vessel. Thecombination was mixed for 30 minutes and then cooled to <40° C. andpackaged off.

Example 3

120 grams of Example 1 were heated to 60° C., placed under agitation andthen 80 grams of glycerin were charged to the vessel. The combinationwas mixed for 30 minutes and then cooled to <40° C. and packaged off.

Example 4

120 grams of Example 1 were heated to 60° C., placed under agitation andthen 40 grams of ethylene glycol and 40 grams of tripropylene glycolmonomethyl ether were charged to the vessel. The combination was mixedfor 30 minutes and then cooled to <40° C. and packaged off.

Example 5

450 grams of ethylene glycol was charged to a vessel, placed understrong agitation and then heated to 60° C. 300 grams of apolysuccinimide (5000 average molecular weight) was then slowly chargedto the vessel and mixed until completely dispersed. The mixture was thenheated to 140° C. and held until all particles dissolved (˜1.5 hrs). Themix was then cooled to 50° C. 147 grams of KOH flakes were slowlycharged to the mix at a rate to maintain temperature of 60-80° C. Theformulation was mixed until all KOH flakes (100%) were dissolved. Themix was then cooled to 40° C. and then placed under high shear agitationby using an overhead mixer equipped with a cowles blade whilemaintaining the batch temperature at 60-80° C. for 1 hour. After onehour, an FTIR scan was run to determine if the presence of ester hadbeen eliminated. The mixture was sampled every 30 minutes until tracesof esters had been eliminated. The mixture was cooled to <30° C. andthen packaged off in an appropriate container.

Example 6

58.54 grams of Example 5 were charged to a vessel and then placed understrong agitation and then heated to 60° C. 65.4 grams of ethylene glycolwere then charged to the vessel and mixed for 30 minutes. After 30minutes, the mixture was cooled to 38° C. and then packaged off in anappropriate container.

Example 7

58.54 grams of Example 5 were charged to a vessel and then placed understrong agitation and then heated to 60° C. 35.4 grams of ethylene glycoland 30 grams of dimethyl glutarate were then charged to the vessel andmixed for 30 minutes. After 30 minutes, the mixture was cooled to 38° C.and then packaged off in an appropriate container.

Example 8

58.54 grams of Example 5 were charged to a vessel and then placed understrong agitation and then heated to 60° C. 65.4 grams of glycerin werethen charged to the vessel and mixed for 30 minutes. After 30 minutes,the mixture was cooled to 38° C. and then packaged off in an appropriatecontainer.

Example 9

104.3 grams of Example 5 were charged to a vessel and then placed understrong agitation and then heated to 60° C. 45.7 grams of ethylene glycolwere then charged to the vessel and mixed for 30 minutes. After 30minutes, the mixture was cooled to 38° C. and then packaged off in anappropriate container.

Example 10

183.12 grams of dimethyl sulfoxide was charged to a vessel, placed understrong agitation and then heated to 60° C. 78.48 grams of apolysuccinimide (5000 average molecular weight) was then slowly chargedto the vessel and mixed until completely dispersed. 72.34 grams of DIwater was charged to the vessel and then 49.07 grams of NH4OH/28% wereslowly charged holding the mixture's temperature at 60-80° C. It wasmixed for one hour and then placed under a vacuum of 50 mm with a slightN₂ sparge until distillation ceases. The mix was then cooled to 40° C.and then packaged off in an appropriate container.

Example 11

282.52 grams of dimethyl sulfoxide was charged to a vessel, placed understrong agitation and then heated to 60° C. 146.23 grams of a partialsodium hydroxide neutralized polyacrylic acid (Kemira 5847) was thencharged to the vessel and mixed for 15 minutes. A vacuum of 38 mm wasapplied until distillation ceases. The mix was then cooled to 40° C. andthen packaged off in an appropriate container.

Example 12

250 grams of ethylene glycol, 250 grams of L-aspartic acid and 2.94grams of phosphoric acid/85% were charged to a vessel, then placed understrong agitation and then heated to 175° C. After 5 hrs. 64.3 grams ofdistillate were collected and the batch was cooled to 60° C. 97.44 gramsKOH flake (100%) was then slowly charged to the vessel at a rate thatallowed the batch temperature to be 60-80° C. and mixed until completelydissolved. It was then placed under high shear agitation by using anoverhead mixer equipped with a cowles blade while maintaining the batchtemperature at 60-80° C. for 1 hour. After one hour, an FTIR scan wasrun to determine if the presence of ester had been eliminated. Themixture was sampled every 30 minutes until traces of esters had beeneliminated. After the ester peak was eliminated, 281.08 grams ofethylene glycol were charged and the resulting mixture was mixed for 30minutes. The mix was then cooled to 40° C. and then packaged off in anappropriate container.

Example 13

71.58 grams of acetone was charged to a vessel and then 12.48 grams ofmaleic anhydride and 16.49 grams itaconic anhydride and 0.98 grams ofbenzoyl peroxide were charged to the vessel. Very slow agitation wasused until the maleic briquettes were dissolved. The vessel was thensealed and inerted with N₂ and the batch was heated to 60° C. and heldat 55-65° C. for five hours. After five hours, the batch was cooled to35° C. and 43.45 grams of ethylene glycol was charged. A vacuum was thenpulled on the vessel slowly decreasing the pressure based on thedistillation rate while heating the batch back to 55-65° C. Whendistillation ceases, the vacuum was broken with N₂ and then 15.39 gramsof KOH flake (100%) were slowly charged in order to hold temperature at60-80° C. When KOH flakes were completely dissolved, the mix was placedunder high shear agitation by using an overhead mixer equipped with acowles blade while maintaining the batch temperature at 60-80° C. for 1hour. Thereafter the mix was checked using an FTIR scan. The FTIR scanwas run and checked every 30 minutes for the disappearance of the esterpeak. After the ester peak disappeared, 89.63 grams of ethylene glycolwere charged, and the batch was then mixed 30 minutes and cooled to <40°C. and then off-loaded into the appropriate container.

Example 14

45 grams of Example 12 were mixed with 10 grams of N-Yield (an ureaseinhibitor in an organic liquid), 40 grams of N-Bound (a nitrificationinhibitor in an organic liquid) and 5 grams of glycerin. The resultingfluid product was then off-loaded into the appropriate container.

The following references are incorporated by reference in theirentireties.

4,839,461 Boehmke 4,172,072 Ashmead 4,799,953 Danzig 4,813,997Kinnersley 4,863,506 Young 5,059,241 Young 5,047,078 Gill 5,350,735Kinnersley 5,593,947 Kinnersley 5,783,523 Koskan 5,814,582 Koskan6,753,395 Sanders 6,756,461 Sanders 6,818,039 Sanders 8,043,995 Sanders8,016,907 Sanders 8,025,709 Sanders

It is contemplated and therefore within the scope of the presentinvention that any feature that is described above can be combined withany other feature that is described above. When mixtures, formulationsand/or compositions are discussed, it should be understood that thosemixtures, formulations and/or compositions are contemplated as beingparts of bigger mixtures, formulations and/or compositions. Further, ifa composition is enumerated, methods using and methods of making thatcomposition are contemplated and within the scope of the presentinvention. When a range is discussed, it is contemplated and thereforewithin the scope of the invention that any number that falls within thatrange is contemplated as an end point generating a plurality ofsub-ranges within that range. For example if a range of 1-10 is given,2, 3, 4, 5, 6, 7, 8, and 9 are contemplated as end points to generate asub-range that fit within the scope of the enumerated range. Moreover,it should be understood that the present invention contemplates minormodifications that can be made to the compositions and methods of thepresent invention. In any event, the present invention is defined by thebelow claims.

We claim:
 1. A composition comprising a) one or more polyorganic acidsand/or their salts, b) organic liquid solvating system, c) one or morenitrification inhibitors and/or one or more urease inhibitors and d) oneor more fertilizers selected from the group consisting of i) fertilizersolids and ii) liquid fertilizers, wherein the organic liquid solvatingsystem and the one or more polyorganic acids and/or their salts are thedelivery formulation for delivering the one or more polyorganic acidsand/or their salts to fertilizer solids and/or liquid fertilizers,wherein the organic liquid solvating system comprises one or moremembers selected from the group consisting of i) protic solvents and ii)aprotic solvents, wherein the one or more protic solvents are selectedfrom the group consisting of: (i) one or more alcohols selected from thegroup consisting of C₁-C₁₀ alkanols, (ii) one or more polyols selectedfrom the group consisting of poly(C₁-C₁₀ alkylene) glycols, (iii) one ormore alkylene glycols selected from the group consisting of ethylene,propylene, and butylene glycol, (iv) one or more members selected fromthe group consisting of glycerin, trimethylol propane, triethanolpropane, and pentaerythritol, (v) one or more alkanolamines selectedfrom the group consisting of: ethanolamine, diethanolamine,dipropanolamine, methyl diethanolamine, monoisopropanolamine andtriethanolamine, and (vi) one or more alkylene glycol alkyl ethersselected from the group consisting of tripropylene glycol methyl ether,and tripropylene glycol butyl ether, wherein the one or more aproticsolvents are selected from the group consisting of (i) dimethylsulfoxide, (ii) dialkyl sulfoxide, diaryl sulfoxide, and an alkylarylsulfoxide having the formulaR₁—SO—R₂, wherein: R₁ is methyl, ethyl, n-propyl, phenyl or benzyl andR₂ is ethyl, n-propyl, phenyl or benzyl, (iii) one or more alkylcarbonates selected from the group consisting of ethylene, propylene andbutylene carbonates, (iv) one or more lactates selected from the groupconsisting of ethyl, propyl, and butyl lactate, (v) isophorone, (vi) oneor more diesters selected from the group consisting ofdimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethylglutarate, wherein the one or more nitrification inhibitors are selectedfrom the group consisting of i) 2-chloro-6-trichloromethyl)pyridine, ii)4-amino-1,2,4,6-triazole-HCl, iii) 2,4-diamino-6-trichloromethyltriazineCL-1580, iv) dicyandiamide, v) thiourea, vi) 1-mercapto-1,2,4-triazole,and vii) 2-amino-4-chloro-6-methylpyrimidine, wherein the one or moreurease inhibitors are selected from the group consisting of i)phosphoric triamides, ii) thiophosphoric triamides, and iii) alkylatedthiophosphoric triamides, wherein the alkylated thiophosphoric triamideshave one or more alkyl groups that independently contain between 1 and 6carbon atoms and wherein the delivery formulation comprises less than 1%water.
 2. The composition of claim 1, wherein said composition is madeby adding said one or more nitrification inhibitors and/or said one ormore urease inhibitors to the one or more fertilizers, wherein the oneor more nitrification inhibitors and/or the one or more ureaseinhibitors are dissolved into said organic liquid solvating system, b)optionally one or more dispersed nitrification inhibitors and/ordispersed urease inhibitors are added to the organic liquid solvatingsystem and c) optionally one or more dispersed nitrification inhibitorsand/or dispersed urease inhibitors are added to the one or morefertilizers.
 3. The composition of claim 1, wherein the one or moreurease inhibitors comprises N-(n-butyl) thiophosphoric triamide.
 4. Thecomposition of claim 1, wherein the composition further comprises thenitrification inhibitor 3,4-dimethylpyrazole phosphate.
 5. Thecomposition of claim 1, wherein the composition of the organic liquidsolvating system further comprises the protic solvent isopropylideneglycerol.
 6. The composition of claim 1, wherein said polyorganic acidsand/or their salts comprise one or more members selected from the groupconsisting of a) monomer, b) homopolymer, c) a copolymer and d) aterpolymer wherein said polyorganic acids comprise one or more membersselected from the group consisting of: i) aspartic acid, ii) glutamicacid, iii) maleic anhydride, iv) itaconic anhydride, v) citraconicanhydride, and vi) acrylic acid wherein the salts of the polyorganicacids are a result of a reaction with one or more neutralizing compoundsselected from the group consisting of: NaOH, KOH, NH₃, K₂CO₃ Na₂CO₃,KHCO₃ and NaHCO₃.
 7. The composition of claim 1, wherein the organicliquid solvating system further comprises one or more members selectedfrom the group consisting of: surfactants, buffers, fragrance/odormasking agents, colorants, micro-nutrients, drying agents, and flowmodifiers.
 8. The composition of claim 1, wherein said fertilizer solidscomprise one or more members selected from the group consisting of a)urea, b) phosphate anion with one or more cations selected from thegroup consisting of i) calcium, ii) magnesium, iii) ammonium iv)manganese, v) zinc, and vi) iron, and c) manure and wherein saidfertilizer solids comprise granules.
 9. The composition of claim 1,wherein the composition of the delivery formulation further comprisesthe polyorganic acid citric acid and/or its salts.
 10. The compositionof claim 1, wherein the composition of said delivery formulationcomprises 5-50% polyorganic acids and/or their salts.
 11. A compositioncomprising a) one or more polyorganic acids and/or their salts, b)organic liquid solvating system, c) one or more inhibitors and d) one ormore ureas selected from the group consisting of i) urea solids and ii)mixtures of liquid ureas, wherein the organic liquid solvating systemand the one or more polyorganic acids and/or their salts are thedelivery formulation for delivering the one or more polyorganic acidsand/or their salts to the surface of said urea solids and/or to saidmixtures of liquid ureas, wherein the organic liquid solvating systemcomprises one or more members from the group consisting of i) proticsolvents and ii) aprotic solvents wherein the one or more proticsolvents are selected from the group consisting of: one or more alcoholsselected from the group consisting of: (i) C₁-C₁₀alkanols, (ii) one ormore polyols selected from the group consisting of poly(C₁-C₁₀ alkylene)glycols, (iii) one or more alkylene glycols selected from the groupconsisting of ethylene, propylene, and butylene glycol, (iv) one or moremembers selected from the group consisting of glycerin, trimethylolpropane, triethanol propane, and pentaerythritol, (v) one or morealkanolamines selected from the group consisting of: ethanolamine,diethanolamine, dipropanolamine, methyl diethanolamine,monoisopropanolamine and triethanolamine, and (vi) one or more alkyleneglycol alkyl ethers selected from the group consisting of tripropyleneglycol methyl ether, and tripropylene glycol butyl ether, wherein theone or more aprotic solvents are selected from the group consisting of(i) dimethyl sulfoxide, (ii) dialkyl sulfoxide, diaryl sulfoxide, and analkylaryl sulfoxide having the formulaR₁—SO—R₂, wherein: R₁ is methyl, ethyl, n-propyl, phenyl or benzyl andR₂ is ethyl, n-propyl, phenyl or benzyl, (iii) one or more alkylcarbonates selected from the group consisting of ethylene, propylene andbutylene carbonates, (iv) one or more lactates selected from the groupconsisting of ethyl, propyl, and butyl lactate, (v) isophorone, (vi) oneor more diesters selected from the group consisting ofdimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethylglutarate, wherein said one or more inhibitors are selected from thegroup consisting of one or more nitrification inhibitors and one or moreurease inhibitors wherein the one or more nitrification inhibitors areselected from the group consisting of i)2-chloro-6-trichloromethyl)pyridine, ii) 4-amino-1,2,4,6-triazole-HCl,iii) 2,4-diamino-6-trichloromethyltriazine CL-1580, iv) dicyandiamide,v) thiourea, vi) 1-mercapto-1,2,4-triazole, and vii)2-amino-4-chloro-6-methylpyrimidine, wherein the one or more ureaseinhibitors are selected from the group consisting of i) phosphorictriamides, ii) thiophosphoric triamides, and iii) alkylatedthiophosphoric triamides, wherein the alkylated thiophosphoric triamideshave one or more alkyl groups that independently contain between 1 and 6carbon atoms and wherein the composition of the delivery formulationcomprises less than 1% water.
 12. The composition claim 11, wherein ofthe composition is made by adding said one or more nitrificationinhibitors and/or said one or more urease inhibitors to the urea,wherein a) one or more nitrification inhibitors and/or one or moreurease inhibitors are dissolved into said organic liquid solvatingsystem, b) optionally one or more dispersed nitrification inhibitorsand/or dispersed urease inhibitors are added to the organic liquidsolvating system and c) optionally one or more dispersed nitrificationinhibitors and/or dispersed urease inhibitors are added to the ureasolids and/or the mixtures of liquid ureas.
 13. The composition of claim11, wherein the one or more urease inhibitors comprises N-(n-butyl)thiophosphoric triamide.
 14. The composition of claim 11, wherein thecomposition further comprises the nitrification inhibitor3,4-dimethylpyrazole phosphate.
 15. The composition of claim 11, whereinthe composition of the organic liquid solvating system further comprisesthe protic solvent isopropylidene glycerol.
 16. The composition of claim11, wherein said polyorganic acids and/or their salts comprise one ormore members selected from the group consisting of a) monomer, b)homopolymer, c) a copolymer and d) a terpolymer wherein said polyorganicacids comprise one or more members selected from the group consistingof: i) aspartic acid, ii) glutamic acid, iii) maleic anhydride, iv)itaconic anhydride, v) citraconic anhydride, and vi) acrylic acidwherein the salts of the polyorganic acids are a result of a reactionwith one or more neutralizing compounds selected from the groupconsisting of: NaOH, KOH, NH₃, K₂CO₃ Na₂CO₃, KHCO₃ and NaHCO₃.
 17. Thecomposition of claim 11, wherein the organic liquid solvating systemfurther comprises one or more members selected from the group consistingof: surfactants, buffers, fragrance/odor masking agents, colorants,micro-nutrients, drying agents, and flow modifiers.
 18. The compositionof claim 11, wherein the composition further comprises citric acidand/or its salts.
 19. The composition of claim 11, wherein thecomposition of said delivery formulation comprises 5-50% polyorganicacids and/or their salts and wherein the composition of the organicliquid solvating system comprises less than 1% water.
 20. Thecomposition of claim 11, wherein the urea solids comprise granules.